Cluster superconductivity in the magnetoelectric Pb(Fe1/2Sb1/2)O3 ceramics

We report the observation of cluster (local) superconductivity in the magnetoelectric Pb(Fe1/2Sb1/2)O3 ceramics prepared at a hydrostatic pressure of 6 GPa and temperatures 1200-1800 K to stabilize the perovskite phase. The superconductivity is manifested by an abrupt drop of the magnetic susceptibility at the critical temperature TC 7 K. Both the magnitude of this drop and TC decrease with magnetic field increase. Similarly, the low-field paramagnetic absorption measured by EPR spectrometer drops significantly below TC as well. The observed effects and their critical magnetic field dependence are interpreted as manifestation of the superconductivity and Meissner effect in metallic Pb nanoclusters existing in the ceramics. Their volume fraction and average size were estimated as 0.1-0.2% and 140-150 nm, respectively. The superconductivity related effects disappear after oxidizing annealing of the ceramics.Comment: 9 pages, 5 figure

Spontaneous and induced ferroelectricity in the BiFe1−xScxO3 perovskite ceramics

High-pressure synthesis method allows obtaining single-phase perovskite BiFe1-xScxO3 ceramics in the entire concentration range. As-prepared compositions with x from 0.30 to 0.55 have the antipolar orthorhombic Pnma structure but can be irreversible converted into the polar rhombohedral R3c or the polar orthorhombic Ima2 phase via annealing at ambient pressure. Microstructure defects and large conductivity of the high-pressure-synthesized ceramics make it difficult to study and even verify their ferroelectric properties. These obstacles can be overcome using piezoresponse force microscopy (PFM) addressing ferroelectric behavior inside single grains. Herein, the PFM study of the BiFe1-xScxO3 ceramics (0.30 ≤ x ≤ 0.50) is reported. The annealed samples show a strong PFM contrast. Switching of domain polarity by an electric field confirms the ferroelectric nature of these samples. The as-prepared BiFe0.5Sc0.5O3 ceramics demonstrate no piezoresponse in accordance with the antipolar character of the Pnma phase. However, application of a strong enough electric field induces irreversible transition to the ferroelectric state. The as-prepared BiFe0.7Sc0.3O3 ceramics show coexistence of ferroelectric and antiferroelectric grains without poling. It is assumed that mechanical stress caused by the sample polishing can be also a driving force of phase transformation in these materials alongside temperature and external electric field.publishe

Magnetic phase transitions in solid solutions of Fe-containing perovskite multiferoics

This study was supported by RFBR (project 18-52-00029_a) and by the Ministry of Education and Science of the Russian Federation (project 3.1649.2017/4.6)

INVESTIGATION OF SORPTION CHARACTERISTICS OF POLYMERIC MINERAL-FILLED COMPOSITES FOR MEDICINE

The polymer compositions on the base of acrylic derivatives and bentonite particles modified by silver ions with various share and dispersion are received and studied by radical polymerization in the water. Partially neutralized acrylic acid, acrylamide and methylene-bis-acrilamide and particles of bentonite with fraction 0 - 0,05 mass.% are chosen as initial substances. The influence of bentonite concentration on absorbing characteristics of polymer materials in the distilled water is shown. It is demonstrated that the increase of bentonite fraction up to 5 mass.% leads to the rise of degree of equilibrium swelling by 1,5 – 2 times in comparison with an unfilled polymer matrix. The acrylic nanocompositions with a mass fraction of bentonite equal to 0,01 mass.% possess the greatest kinetic characteristics. Kinetic dependences of new composite materials swelling in physiological solution from a filler dispersion part are investigated. It is shown that in high dispersion (with particle size less than 0,25 mm) a part of mineral–containing filler equal to 1 mass.% leads to significant increase in values of equilibrium swelling degree in comparison with an unfilled sample (by 1,5 times). The effect of polyelectrolyte suppression of polymer composition swelling in physiological solution is studied. It results in values reduction of equilibrium swelling degree in comparison with these values in the distilled water. Application prospects for the received compositions are shown at bandages creation for wounds treatment of various etiologies. Research results are recommended for usage in medical practice for optimization of wound process march

ДИЭЛЕКТРИЧЕСКИЕ СВОЙСТВА СЕГНЕТОЭЛЕКТРИЧЕСКОЙ КЕРАМИКИ СИСТЕМЫ ТВЕРДЫХ РАСТВОРОВ (1–x)(NaBi)1/2TiO3 – xBiCoO3

The solid solutions with the rhombohedral distorted perovskite structure of the (1–x)(NaBi)1/2TiO3–xBiCoO3 system (x < 0.2) have been prepared by solid state reactions. The unit cell parameters aH and cH for these perovscites were found to increase linearly with increasing x. The dielectric properties of the solid solutions undergo a diffuse ferroelectric phase transition at 590–610 K. For compositions with x < 0.05, the transition to relaxor state at a temperature below 500 K was observed. At x > 0.05 such a transition was not revealed.Методом твердофазных реакций синтезирована керамика системы (1–x)(NaBi)1/2TiO3–xBiCoO3. Установлено, что в данной системе в области составов х ≤ 0,2 образуются твердые растворы (ТР) с ромбоэдрической структурой. Определены структурные характеристики ТР данной системы. Показано, что параметры гексагональной элементарной ячейки aH и cH линейно возрастают с увеличением х. Приводятся результаты исследования диэлектрических свойств керамики полученных ТР. Установлено, что керамика проявляет свойства сегнетоэлектрика с размытым фазовым пере- ходом. При увеличении содержания BiCoO3 в системе (х > 0,05) имеющий место для (NaBi)1/2TiO3 при Т < 500 К переход в релаксорное состояние для ТР вырождается

Phase formation in the (1- y )BiFeO 3 - y BiScO 3 system under ambient and high pressure

Formation and thermal stability of perovskite phases in the BiFe1-yScyO3 system (0≤y≤0.70) were studied. When the iron-to-scandium substitution rate does not exceed about 15 at%, the single-phase perovskite ceramics with the rhombohedral R3c symmetry (as that of the parent compound, BiFeO3) can be prepared from the stoichiometric mixture of the respective oxides at ambient pressure. Thermal treatment of the oxide mixtures with a higher content of scandium results in formation of two main phases, namely a BiFeO3-like R3c phase and a cubic (I23) sillenite-type phase based on γ-Bi2O3. Single-phase perovskite ceramics of the BiFe1-yScyO3 composition were synthesized under high pressure from the thermally treated oxide mixtures. When y is between 0 and 0.25 the high-pressure prepared phase is the rhombohedral R3c with the √2ap×√2ap×2√3ap superstructure (ap ~ 4 Å is the pseudocubic perovskite unit-cell parameter). The orthorhombic Pnma phase (√2ap×4ap×2√2ap) was obtained in the range of 0.30≤y≤0.60, while the monoclinic C2/c phase (√6ap×√2ap×√6ap) is formed when y=0.70. The normalized unit-cell volume drops at the crossover from the rhombohedral to the orthorhombic composition range. The perovskite BiFe1-yScyO3 phases prepared under high pressure are metastable regardless of their symmetry. At ambient pressure, the phases with the compositions in the ranges of 0.20≤y≤0.25, 0.30≤y<0.50 and 0.50≤y≤0.70 start to decompose above 970, 920 and 870 K, respectivelypublishe

Magnetic behaviour of perovskite compositions derived from BiFeO3

The phase content and sequence, the crystal structure, and the magnetic properties of perovskite solid solutions of the (1−y)BiFeO3–yBiZn0.5Ti0.5O3 series (0.05 ≤ y ≤ 0.90) synthesized under high pressure have been studied. Two perovskite phases, namely the rhombohedral R3c and the tetragonal P4mm, which correspond to the structural types of the end members, BiFeO3 and BiZn0.5Ti0.5O3, respectively, were revealed in the as-synthesized samples. The rhombohedral and the tetragonal phases were found to coexist in the compositional range of 0.30 ≤ y ≤ 0.90. Magnetic properties of the BiFe1−y [Zn0.5Ti0.5]yO3 ceramics with y < 0.30 were measured as a function of temperature. The obtained compositional variations of the normalized unit-cell volume and the Néel temperature of the BiFe1−y [Zn0.5Ti0.5]yO3 perovskites in the range of their rhombohedral phase were compared with the respective dependences for the BiFe1−yB 3+yO3 perovskites (where B 3+ = Ga, Co, Mn, Cr, and Sc). The role of the high-pressure synthesis in the formation of the antiferromagnetic states different from the modulated cycloidal one characteristic of the parent BiFeO3 is discussed.publishe

Exchange bias effect in bulk multiferroic BiFe0.5Sc0.5O3

Below the Néel temperature, TN ∼ 220 K, at least two nano-scale antiferromagnetic (AFM) phases coexist in the polar polymorph of the BiFe0.5Sc0.5O3 perovskite; one of these phases is a weak ferromagnetic. Non-uniform structure distortions induced by high-pressure synthesis lead to competing AFM orders and a nano-scale spontaneous magnetic phase separated state of the compound. Interface exchange coupling between the AFM domains and the weak ferromagnetic domains causes unidirectional anisotropy of magnetization, resulting in the exchange bias (EB) effect. The EB field, HEB, and the coercive field strongly depend on temperature and the strength of the cooling magnetic field. HEB increases with an increase in the cooling magnetic field and reaches a maximum value of about 1 kOe at 5 K. The exchange field vanishes above TN with the disappearance of long-range magnetic ordering. The effect is promising for applications in electronics as it is large enough and as it is tunable by temperature and the magnetic field applied during cooling.publishe

Multiferroic Bi 0.65 La 0.35 Fe 0.5 Sc 0.5 O 3 perovskite:Magnetic and thermodynamic properties

Magnetic and thermodynamic properties of polycrystalline multiferroic Bi 0.65 La 0.35 Fe 0.5 Sc 0.5 O 3 synthesized under high-pressure and high-temperature conditions are reported. Magnetic properties were studied using a SQUID magnetometer technique over the temperature range of 5−300 K in magnetic fields up to H=10 kOe. The field dependent magnetization M(H) was measured in magnetic fields up to 50 kOe at different temperatures up to 230 K after zero-field cooling procedure. A long-range magnetic ordering of the AFM type with a weak FM contribution occurs below the Néel temperature T N ~237 K. Magnetic hysteresis loops taken below T N show a huge coercive field up to H c ~10 kOe. A strong effect of magnetic field on the magnetic properties of the compound has been found. Derivative of the initial magnetization curves demonstrates a temperature-dependent anomaly in fields of H=15−25 kOe. Besides, an anomaly of the temperature dependent zero-field cooled magnetization measured in magnetic fields of 6−7 kOe has been found. Origin of both anomalies is associated with inhomogeneous magnetic state of the compound. The heat capacity has been measured from 2 K up to room temperature and a significant contribution from the magnon excitations at low temperatures has been detected. From the low-temperature heat capacity, an anisotropy gap of the magnon modes of the order 3.7 meV and Debye temperature T D =189 K have been determined

Polar and antipolar polymorphs of metastable perovskite BiFe0.5Sc0.5O3

A metastable perovskite BiFe0.5Sc0.5O3 synthesized under high-pressure (6 GPa) and high-temperature (1500 K) conditions was obtained in two different polymorphs, antipolar Pnma and polar Ima2, through an irreversible behavior under a heating/cooling thermal cycling. The Ima2 phase represents an original type of a canted ferroelectric structure where Bi3+ cations exhibit both polar and antipolar displacements along the orthogonal [110](p) and [1 (1) over bar0](p) pseudocubic directions, respectively, and are combined with antiphase octahedral tilting about the polar axis. Both the Pnma and the Ima2 structural modifications exhibit a long-range antiferromagnetic ordering with a weak ferromagnetic component below T-N similar to 220 K. Analysis of the coupling between the dipole, magnetic, and elastic order parameters based on a general phenomenological approach revealed that the weak ferromagnetism in both phases is mainly caused by the presence of the antiphase octahedral tilting whose axial nature directly represents the relevant part of Dzyaloshinskii vector. The magnetoelectric contribution to the spontaneous magnetization allowed in the polar Ima2 phase is described by a fifth-degree free-energy invariant and is expected to be small